Uv curable interplayer for electronic printing

ABSTRACT

UV-curable interlayer compositions are provided. In embodiments, the interlayer composition comprises at least one aliphatic di(meth)acrylate monomer diluent having a dynamic viscosity at 25° C. of less than about 100 cps; at least one (meth)acrylate oligomer selected from epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates and combinations thereof, the at least one(meth) acrylate oligomer having a glass transition temperature in the range of from about minus 10° C. to about 100° C. and a dynamic viscosity at 25° C. of less than about 3000 cps; and at least two photoinitiators. Multilayer structures formed using the compositions and related methods are also provided.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser.No. 15/227,442, filed Aug. 3, 2016, which is incorporated herein byreference in its entirety

BACKGROUND

Fabrication of electronic circuit elements using liquid depositiontechniques is of profound interest as such techniques providepotentially low-cost alternatives to conventional mainstream amorphoussilicon technologies for electronic applications such as thin filmtransistors (TFTs), light-emitting diodes (LEDs), radio frequencyidentification (RFID) tags, photovoltaics, and the like. However, thedeposition and/or patterning of functional electrodes, pixel pads, andconductive traces, lines and tracks which meet the conductivity,processing, and cost requirements for practical applications have beenchallenging.

Solution-processable conductive inks, including metal nanoparticle inks,are of great interest for fabricating such electronic circuit elements.For example, silver nanoparticle inks are a promising class of materialsfor printed electronics. In this regard, fabrication of electroniccircuit elements using silver nanoparticle inks has been described in,for example, U.S. Pat. Nos. 8,765,025; 8,361,350; 8,324,294; 8,298,314;8,158,032; 8,057,849; and 7,270,694, each of which is herebyincorporated by reference in its entirety. However, one issueencountered with metal nanoparticle inks, including silver nanoparticleinks, is a trade-off between the electrical conductivity of the sinteredmetal nanoparticles and their adhesion to the underlying substrate,e.g., a highly conductive layer of sintered metal nanoparticles may havevery poor adhesion. Simply rubbing and/or contacting the surface of theprinted metal features formed from such metal nanoparticle inks candamage the features, thus limiting their functionality and utility inthe electronic devices. The issue of adhesion has been previouslyaddressed by the adjusting the composition of the metal nanoparticleinks and/or the use of thermally curable interlayer compositions.Thermally curable interlayer compositions typically require high curingtemperatures (e.g., from about 120° C. to about 150° C.) and long curingtimes (e.g., from about 2 hours to about 5 hours).

SUMMARY

The present disclosure, which enables curing at lower temperatures orfor less time, accordingly provides illustrative examples of interlayercompositions, interlayer films, and multilayer structures containingthese interlayer films, as well as associated methods of producing theseinterlayer compositions and films, and their assembled multilayerstructures.

In one aspect, a UV-curable interlayer composition is provided. Inembodiments, the interlayer composition comprises at least one aliphaticdi(meth)acrylate monomer diluent having a dynamic viscosity at 25° C. ofless than about 100 cps; at least one (meth)acrylate oligomer selectedfrom epoxy (meth)acrylates, polyester (meth)acrylates, polyether(meth)acrylates, urethane (meth)acrylates and combinations thereof, theat least one(meth) acrylate oligomer having a glass transitiontemperature in the range of from about minus 10° C. to about 100° C. anda dynamic viscosity at 25° C. of less than about 3000 cps; and at leasttwo photoinitiators.

In another aspect, a multilayer structure is provided. In embodiments,the multilayer structure comprises a substrate; an interlayer film onthe substrate, and a conductive layer on the interlayer film, theconductive layer comprising sintered metal nanoparticles. The interlayerfilm is formed from a UV curable interlayer composition comprising atleast one aliphatic di(meth)acrylate monomer diluent having a dynamicviscosity at 25° C. of less than about 100 cps; at least one(meth)acrylate oligomer selected from epoxy (meth)acrylates, polyester(meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates andcombinations thereof, the at least one(meth) acrylate oligomer having aglass transition temperature in the range of from about minus 10° C. toabout 100° C. and a dynamic viscosity at 25° C. of less than about 3000cps; and at least two photoinitiators.

In another aspect, a process of forming a multilayer structure isprovided. In embodiments, the process comprises depositing a UV-curableinterlayer composition on a substrate; exposing the deposited interlayercomposition to UV light under conditions sufficient to cure theinterlayer composition to form a cured interlayer film; depositing aconductive composition comprising metal nanoparticles on the curedinterlayer film; and annealing the conductive composition to produce aconductive layer comprising sintered metal nanoparticles. The interlayercomposition comprises at least one aliphatic di(meth)acrylate monomerdiluent having a dynamic viscosity at 25° C. of less than about 100 cps;at least one (meth)acrylate oligomer selected from epoxy(meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates,urethane (meth)acrylates and combinations thereof, the at least one(meth)acrylate oligomer having a glass transition temperature in therange of from about minus 10° C. to about 100° C. and a dynamicviscosity at 25° C. of less than about 3000 cps; and at least twophotoinitiators.

These and other aspects will be discussed in greater detail below.

DETAILED DESCRIPTION

The present disclosure provides interlayer compositions, interlayerfilms, multilayer structures containing the interlayer films, andrelated methods. The interlayer compositions are curable usingultraviolet (UV) light to provide the interlayer films. In embodiments,the interlayer films are produced more efficiently (e.g., less than aminute) under conditions (e.g., room temperature) which are morecompatible with processing techniques for electronic devices (e.g., inkjet printing), by contrast to thermally curable interlayer compositions.Moreover, in embodiments, the interlayer films provide excellentadhesion of conductive layers (e.g., those containing sintered silvernanoparticles) to an underlying substrate (e.g., glass or a flexiblepolymeric substrate), while maintaining the conductivity and mechanicalrobustness of such conductive layers.

Interlayer Composition

In embodiments, the interlayer composition contains at least onemulti-functional (meth)acrylate monomer diluent, at least one(meth)acrylate oligomer, and at least one photoinitiator.

A variety of multi-functional (meth)acrylate monomer diluents may beused. Combinations of different types of multi-functional (meth)acrylatemonomer diluents may be used. As used throughout this specification theterm “(meth)acrylate” encompasses both methacrylate and acrylatecompounds. In other embodiments, the interlayer composition contains asingle type of multi-functional (meth)acrylate monomer diluent. Suitablemulti-functional (meth)acrylate monomer diluents include di-functional(meth)acrylate monomer diluents such as aliphatic di(meth)acrylates. Thealiphatic portion of these monomer diluents may include saturated orunsaturated bonds and may be linear, branched or cyclic. For example,di-functional aliphatic (meth)acrylates containing a cyclic structuremay be used. The number of carbon atoms in the aliphatic portion mayvary, for example, in the range of from 2 to 48, in embodiments from 2to 38, in embodiments from 2 to 28, or in embodiments from 2 to 22.

Suitable aliphatic di(meth)acrylates include alkoxylated neopentylglycol di(meth)acrylates. In such alkoxylated neopentyl glycoldi(meth)acrylates, the number of carbon atoms in the aliphatic portionmay vary, for example, in the range of from 7 to 17, from 7 to 13, orfrom 9 to 11. Alkoxylated neopentyl glycol di(meth)acrylates such asethoxylated neopentyl glycol di(meth)acrylate and propoxylated neopentylglycol di(meth)acrylate may be used. Other aliphatic di(meth)acrylatesinclude alkyldiol di(meth) acrylates. In such alkyldiol di(meth)acrylates, the number of carbon atoms in the alkyldiol portion may vary,for example, in the range of from 4 to 20, from 6 to 18, or from 6 to12. The alkyl portion may be linear, branched or cyclic. Alkyldioldi(meth)acrylates such as hexanediol di(meth)acrylate, decanedioldi(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate may beused. Alkoxylated versions of these alkyldiol di(meth)acrylates may beused (e.g., alkoxylated hexanediol di(meth)acrylate), in which case thenumber of carbon atoms in entire aliphatic portion may vary as describedabove. Other aliphatic di(meth)acrylates include alkyl glycoldi(meth)acrylates. In such alkyl glycol di(meth)acrylates, the number ofcarbon atoms in the alkyl portion may vary, for example, in the range offrom 2 to 12, from 2 to 10, or from 2 to 6. Alkyl glycoldi(meth)acrylates such as tripropylene glycol di(meth)acrylate,dipropylene glycol di(meth)acrylate, and ethylene glycoldi(meth)acrylate may be used.

Di-functional aliphatic (meth)acrylates available from Sartomer Co.,Inc., may be used, including propoxylated neopentyl glycol diacrylate(SR9003B), 1,6-hexanediol diacrylate (SR238B), alkoxylated aliphaticdiacrylate (SR9209A), alkoxylated hexanediol diacrylate (CD564), and1,3-butylene glycol dimethacrylate (SR297).

In embodiments, the multi-functional (meth)acrylate monomer diluent hasa molecular weight in the range of from about 100 g/mol to about 1000g/mol, in embodiments, of from about 150 g/mol to about 800 g/mol, or inembodiments of from about 200 g/mol to about 600 g/mol. In embodiments,the multi-functional (meth)acrylate monomer diluent has a dynamicviscosity at 25° C. of less than about 100 cps, in embodiments less than50 cps, in embodiments less than about 20 cps. This includes embodimentsin which the multi-functional (meth)acrylate monomer diluent has adynamic viscosity at 25° C. in the range of from about 3 cps to about100 cps, in embodiments of from about 5 cps to about 80 cps, inembodiments of from about 7 cps to about 60 cps, or in embodiments fromabout 7 cps to about 20 cps.

The multi-functional (meth)acrylate monomer diluent may be provided inthe interlayer composition in various suitable amounts. The amount maybe selected to adjust the dynamic viscosity of the interlayercomposition so that the composition can be deposited using thetechniques described below (e.g., printing, spin coating). Inembodiments, the multi-functional (meth)acrylate monomer diluent ispresent in an amount of from about 50% to about 95% by weight of theinterlayer composition, in embodiments of from about 55% to about 90% byweight of the interlayer composition, in embodiments of from about 60%to about 85% by weight of the interlayer composition, or in embodimentsof from about 65% to about 80% by weight of the interlayer composition.

The interlayer composition may include other multi-functional(meth)acrylate monomer diluents such as tri-functional aliphatic(meth)acrylates, tetra-functional aliphatic (meth)acrylates andpenta-functional aliphatic (meth)acrylates. Suitable tri-functionalaliphatic (meth)acrylates include aliphatic tri(meth)acrylates such as,for example, trimethylolpropane tri(meth)acrylate, glycerol propoxylatetri(meth)acrylate, tris(2-hydroxy ethyl) isocyanurate tri(meth)acrylate,propoxylated trimethylolpropane tri(meth)acrylate, ethoxylatedtrimethylolpropane tri(meth)acrylate, and the like. Tri-functionalaliphatic (meth)acrylates available from Sartomer Co., Inc., may beused, including ethoxylated (3) trimethylolpropane triacrylate (SR454),ethoxylated (6) trimethylolpropane triacrylate (SR499), ethoxylatedtrimethylolpropane triacrylate (SR455LM), trimethylolpropane triacrylate(SR351LV), and propoxylated (3) trimethylolpropane triacrylate (SR492).

Suitable tetra-functional aliphatic (meth)acrylates includedi-trimethylolpropane tetraacrylate (available from Sartomer Co., Inc asSR355), ethoxylated (4) pentaerythritol tetraacrylate (available fromSartomer Co., Inc. as SR494), and pentaerythritol tetraacrylate(available from Sartomer Co., Inc. as SR295). Suitable penta-functionalaliphatic (meth)acrylates include dipentaerythritol pentaacrylate(available from Sartomer Co., Inc. as SR399) and pentaacrylate ester(available from Sartomer Co., Inc. as SR9041).

When tri-functional aliphatic (meth)acrylates, tetra-functionalaliphatic (meth)acrylates and/or penta-functional aliphatic(meth)acrylates are included in the interlayer compositions, inembodiments, they may be included in an amount of no more than about 5%by weight of the interlayer composition, no more than about 3% by weightof the interlayer composition, no more than about 1% by weight of theinterlayer composition or no more than about 0.5% by weight of theinterlayer composition.

A variety of (meth)acrylate oligomers may be used. The (meth)acrylateoligomer may be selected to improve film formation and crosslinkingwithin the interlayer and to improve the adhesion of the interlayer filmformed from the composition to an underlying substrate. Suitable(meth)acrylate oligomers include epoxy (meth)acrylates, polyester(meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates andcombinations thereof. Suitable acrylate oligomers include SD-5907 andSD-661, available from DIC Imaging Corporation. Although in embodimentscombinations of different types of (meth)acrylate oligomers are used, inother embodiments, the interlayer composition contains a single type of(meth)acrylate oligomer.

In embodiments, the (meth)acrylate oligomer has a number averagemolecular weight M_(n) in the range of from about 300 to about 3000, inembodiments, of from about 500 to about 2500, in embodiments of fromabout 1000 to about 2000, in embodiments of from about 1950 to about3000, in embodiments of from about 2450 to about 3000, in embodiments offrom about 450 to about 2500, in embodiments of from about 450 to about2000, in embodiments of from about 450 to about 1500, or in embodimentsof from about 450 to about 1000. In embodiments, the (meth)acrylateoligomer has a dynamic viscosity at 25° C. of less than about 3000 cps,in embodiments less than about 1250 cps, or in embodiments less thanabout 1500. This includes embodiments in which the (meth)acrylateoligomer has a dynamic viscosity at 25° C. in the range of from about100 cps to about 3000 cps, in embodiments from about 100 cps to about2000 cps, in embodiments of from about 100 cps to about 1000 cps. Inembodiments, the (meth)acrylate oligomer has a glass transitiontemperature, T_(g), of less than about 100° C., in embodiments less thanabout 70° C., in embodiments less than about 40° C., or in embodimentsless than about 10° C. This includes embodiments in which the T_(g) isin the range of from about −10° C. to about 100° C., from about 0° C. toabout 50° C., or from about 25° C. to about 35° C.

The (meth)acrylate oligomer may be provided in the interlayercomposition in various suitable amounts. In embodiments, the(meth)acrylate oligomer is present in an amount of from about 1% toabout 27% by weight of the interlayer composition, in embodiments offrom about 3% to about 24% by weight of the interlayer composition, inembodiments of from about 6% to about 18% by weight of the interlayercomposition, in embodiments of from about 12% to about 15% by weight ofthe interlayer composition, or embodiments of from about 3% to about 10%by weight of the interlayer composition.

The interlayer composition may include various ratios of themulti-functional (meth)acrylate monomer diluent to the (meth)acrylateoligomer. In embodiments, the ratio of the multi-functional(meth)acrylate monomer diluent to the (meth)acrylate oligomer is in therange of from about 4 to about 16, from about 5 to about 14, from about6 to about 12, or from about 9 to about 15.

A variety of photoinitiators may be used. Combinations of differenttypes of photoinitiators may be used. In embodiments, two differenttypes of photoinitiators are used. For example, a first photoinitiatorselected to facilitate curing of the surface of the interlayercomposition and a second photoinitiator selected to facilitate curing ofthe interlayer composition throughout its thickness (i.e., “depth ofcure”) may be used. The photoinitiator may be selected to haveabsorbance or an absorbance maximum within a particular range ofultraviolet wavelengths, in embodiments from about 100 nm to about 425nm. Suitable photoinitiators include 1-hydroxycyclohexyl phenyl ketone;2,2-dimethoxy-2-phenylacetophenone;2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone;2,4-dimethylthioxanthone; 2,4-diisopropylthioxanthone;isopropylthioxanthone; 2,4,6 Trimethylbenzoyldiphenylphosphine oxide(TPO); bis(2,6-dimethoxybenzoyl)-2,4,4 trimethylpentylphosphine oxide;and the like. The photoinitiators Irgacure-184 and Irgacure TPO-L,available from BASF, may be used.

The photoinitiator may be provided in the interlayer composition invarious suitable amounts. In embodiments, the photoinitiator is presentin an amount of from about 1% to about 20% by weight of the interlayercomposition, in embodiments of from about 1% to about 15% by weight ofthe interlayer composition, in embodiments of from about 1% to about 12%by weight of the interlayer composition, or in embodiments of from about2% to about 12% by weight of the interlayer composition. In embodimentsin which two photoinitiators are used, a first photoinitiator (e.g., oneselected to facilitate surface curing) may be present in an amount offrom about 1% to about 10% by weight of the interlayer composition, inembodiments of from about 1% to about 8% by weight of the interlayercomposition, or in embodiments of from about 2% to about 8% by weight ofthe interlayer composition. In such embodiments, the secondphotoinitiator (e.g., one selected to facilitate depth of cure) may bepresent in an amount of from about 0.5% to about 5% by weight of theinterlayer composition, in embodiments of from about 0.5% to about 2.5%by weight of the interlayer composition, or in embodiments of from about0.5% to about 2% by weight of the interlayer composition.

The interlayer composition may include a variety of additional, optionalcomponents. In embodiments, the interlayer composition includes asurface leveling agent to adjust the surface tension of the interlayercomposition. A variety of surface leveling agents may be used andselected depending upon the choice of the other components of theinterlayer composition. Combinations of different types of surfaceleveling agents may be used. Suitable surface leveling agents includesilicone modified polyacrylate, polyester modified polydimethylsiloxane,polyether modified polydimethylsiloxane, polyacrylate modifiedpolydimethylsiloxane, polyester polyether modified polydimethylsiloxane,low molecular weight ethoxylated polydimethylsiloxane, polyestermodified polymethylalkylsiloxane, polyether modifiedpolymethylalkylsiloxane, aralkyl modified polymethylalkylsiloxane,polyether modified polymethylalkylsiloxane, and the like.

The surface leveling agent may be a polysiloxane copolymer that includesa polyester modified polydimethylsiloxane, commercially available fromBYK Chemical with the trade name of BYK® 310; a polyether modifiedpolydimethylsiloxane, commercially available from BYK Chemical with thetrade name of BYK® 330; a polyacrylate modified polydimethylsiloxane,commercially available from BYK Chemical with the trade name ofBYK®-SILCLEAN 3700 (about 25 weight percent in methoxypropylacetate); ora polyester polyether modified polydimethylsiloxane, commerciallyavailable from BYK Chemical with the trade name of BYK® 375. The surfaceleveling agent may be a low molecular weight ethoxylatedpolydimethylsiloxane with the trade name Silsurf® A008 available fromSiltech Corporation. Other surface leveling agents commerciallyavailable from BYK Chemical may be used as follows: BYK® 377(Polyether-modified, hydroxy-functional polydimethylsiloxane), BYK® 3455(Polyether-modified polydimethylsiloxane), BYK® 9077 (Highmolecular-weight copolymer with pigment affinic groups), BYK®-UV3500(Polyether-modified, acryl-functional polydimethylsiloxane), BYK®-UV3510(Polyether-modified polydimethylsiloxane), and BYK®-UV3505 andBYK®-UV3575 (multi-acrylic functional, modified polydimethylsiloxane).

The surface leveling agent may be provided in the interlayer compositionin various suitable amounts. In embodiments, the surface leveling agentis present in an amount of from about 0.01% to about 3% by weight of theinterlayer composition, in embodiments from about 0.1% to about 2% byweight of the interlayer composition, or in embodiments from about 0.5%to about 1% by weight of the interlayer composition.

Other additional, optional components include curing accelerators,surfactants or combinations thereof.

Another additional component includes one or more types ofmono-functional (meth)acrylate monomers. If present, these may beincluded in an amount of from about 0.5% to about 18% by weight of theinterlayer composition, in embodiments from about 2% to about 16% byweight of the interlayer composition, in embodiments from about 4% toabout 12% by weight of the interlayer composition, in embodiments fromabout 8% to about 10% by weight of the interlayer composition, or inembodiments from about 2% to about 10% by weight of the interlayercomposition.

In embodiments, the interlayer composition consists or consistsessentially of one or more types of multi-functional (meth)acrylatemonomer diluents, one or more types of (meth)acrylate oligomers, one ormore types of photoinitiators, optionally, one or more types of surfaceleveling agents, optionally, one or more types of curing accelerators,optionally, one or more types of surfactants, optionally one or moretypes of mono-functional (meth)acrylate monomer diluents. In otherembodiments, the interlayer composition consists or consists essentiallyof one or more types of multi-functional (meth)acrylate monomerdiluents, one or more types of (meth)acrylate oligomers, one or moretypes of photoinitiators, and one or more types of mono-functional(meth)acrylate monomer diluents.

In embodiments, the interlayer composition does not include a solvent,e.g., an organic solvent.

The interlayer composition may be formed by combining and mixing theselected components in a suitable container.

The interlayer composition may be characterized by its dynamic viscosityat 25° C. In embodiments, the interlayer composition has a dynamicviscosity at 25° C. in the range of from about 10 cps to about 500 cps,in embodiments of from about 10 cps to about 250 cps, or in embodimentsfrom about 10 cps to about 100 cps. The dynamic viscosity of theinterlayer composition may be measured using a commercially availablerheometer (e.g., Ares-G2 from TA Instruments).

The interlayer composition may be characterized by its surface tensionat 25° C. In embodiments, the interlayer composition has a surfacetension at 25° C. in the range of from about 22 mN/m to around 40 mN/m,in embodiments from about 23 mN/m to about 42 mN/m, in embodiments fromabout 25 mN/m to about 38 mN/m, or in embodiments from about 28 mN/m toabout 35 mN/m. The surface tension of the interlayer composition may bemeasured using a commercially available tensiometer (e.g., ForceTensiometer K100 from KRUSS GmbH).

The interlayer composition may be characterized by one or more of theproperties described above, i.e., one or more of dynamic viscosity andsurface tension.

Interlayer Film

The interlayer composition may be used to form an interlayer film whichfacilitates the adhesion of other material layers, including conductivelayers, to an underlying substrate. The interlayer film may be formed bydepositing the interlayer composition on or over a substrate andexposing the deposited interlayer composition to ultraviolet (UV) lightunder conditions sufficient to cure the interlayer composition to formthe interlayer film.

The interlayer composition may be deposited onto the substrate by avariety of techniques, including solution-based deposition techniquessuch as spin coating, dip coating, spray coating, slot die coating,flexographic printing, offset printing, screen printing, gravureprinting, aerosol printing, ink jet printing, and the like. A variety ofsubstrates may be used. Suitable substrates include those composed ofsilicon, glass, polyester, polycarbonate, polyethylene terephthalate(PET), polyimide, polyethylene naphthalate (PEN), and the like. Fabricand synthetic paper substrates may also be used. The material and thethickness of the substrate may be selected such that the substrate has adesired flexibility or rigidity.

The curing conditions include, for example, the wavelength of the UVlight, the curing temperature, the curing time (which may be adjusted bythe curing speed, e.g., when the source of the UV light is scanned overthe deposited interlayer composition), and the curing atmosphere.Various UV wavelengths may be used. In embodiments, the UV wavelength isin the range of from about 100 nm to about 425 nm, in embodiments fromabout 200 nm to about 410 nm, or in embodiments from about 300 nm toabout 410 nm. Any light source providing wavelengths within these rangesmay be used, e.g., mercury arc lamps. In embodiments, the curingtemperature is room temperature, i.e., from about 20° C. to about 25° C.In embodiments, the curing time is less than about 10 minutes, inembodiments less than about 5 minutes, or in embodiments, less thanabout 1 minute. This includes embodiments in which the curing time is inthe range of about 30 seconds to about 10 minutes. The curing may beperformed in air, in an inert atmosphere, for example, under nitrogen orargon, or in a reducing atmosphere, for example, under nitrogencontaining from about 1% to about 20% by volume hydrogen. The curing maybe performed under normal atmospheric pressure, or at a superatmosphericpressure of, for example, from 2 to 500 atmospheres, or at a reducedpressure of, for example, about 1000 mbars to about 0.01 mbars.

The cured interlayer composition, i.e., the interlayer film, may becharacterized by its average thickness. By “average thickness” it ismeant the average value of the thickness of the interlayer film acrossits surface. In embodiments, the average thickness of the interlayerfilm is less than about 15 μm, in embodiments less than about 10 μm, inembodiments less than about 5 μm, in embodiments less than about 1 μn,or in embodiments less than about 800 nm. This includes embodiments inwhich the average thickness of the interlayer film is in the range offrom about 200 nm to about 15 μm or from about 800 nm to about 15 μm.Thus, the interlayer films provided by the present disclosure are quitethin. As demonstrated by the Examples below, despite their thinness, theinterlayer films that have been formed adhere well to underlyingsubstrates and overlying conductive layers.

The interlayer film may be characterized by its glass transitiontemperature, T_(g). In embodiments, the T_(g) is less than about 100°C., in embodiments less than about 70° C., in embodiments less thanabout 40° C. This includes embodiments in which the T_(g) is in therange of from about −10° C. to about 100° C., from about 0° C. to about50° C., from about 20° C. to about 40° C., or from about 25° C. to about35° C. The glass transition temperature of the interlayer film may bemeasured using modulated differential scanning calorimetry on acommercially available differential scanning calorimeter (e.g.,Discovery DSC 2500 from TA Instruments).

The interlayer film may be characterized by its Young's modulus at roomtemperature. In embodiments, the Young's modulus is less than about 1kgf/mm², in embodiments less than about 0.8 kgf/mm², or in embodimentsless than about 0.6 kgf/mm². This includes embodiments in which theYoung's modulus is in the range of from about 0.2 kgf/mm² to about 1kgf/mm². The Young's modulus of the interlayer film may be measured bydynamic mechanical analysis. For example, the interlayer film may be cutinto a “dog-bone” shaped piece suitable for analysis on a commerciallyavailable tensile testing instrument such as an Instron® tensile testinginstrument.

The interlayer film may be characterized by its surface free energy at25° C. In embodiments, the interlayer film has a surface free energy at25° C. in the range of from about 22 mN/m to around 40 mN/m, inembodiments from about 23 mN/m to about 43 mN/m, in embodiments fromabout 25 mN/m to about 38 mN/m, or in embodiments from about 28 mN/m toabout 35 mN/m. The surface free energy of the interlayer film may bemeasured using a commercially available tensiometer (e.g., ForceTensiometer K100 from KRUSS GmbH).

The interlayer film may be characterized by its surface roughness, usinga suitable surface roughness parameter such as Ra, Rz, Rq, Rsk, and thelike. In embodiments, the surface roughness, determined using thesurface roughness parameter Ra (see, e.g., U.S. Pat. No. 9,333,742hereby incorporated by reference in its entirety), is less than about±10 nm, less than about ±5 nm, or less than about ±2 nm. These valuesare indicative of a uniform, smooth surface. The surface roughnessparameters may be measured by a commercially available profilometer suchas a Nanovea® Profilometer.

The interlayer film may be characterized by its instant water contactangle at room temperature. In embodiments, the water contact angle is inthe range of from about 45 degrees to about 105 degrees, in embodimentsfrom about 55 degrees to about 95 degrees, or in embodiments from about65 degrees to about 85 degrees. The instant water contact angle may bemeasured by a commercially available contact angle analyzer such as FTADynamic Contact Angle Analyzer, DAT Instruments USA.

The interlayer film may be characterized by one or more of theproperties described above, i.e., one or more of an average thickness,glass transition temperature. Young's modulus, surface free energy,surface roughness, and instant water contact angle. The particularselection of components and relative amounts of such components of theinterlayer film may be adjusted to achieve one or more of theseproperties.

Multilayer Structure

As described above, the interlayer film may be used to facilitate theadhesion of other material layers, including conductive layers, to anunderlying substrate. Thus, the interlayer film may be part of amultilayer structure. In embodiments, the multilayer structure includesthe substrate, the interlayer film disposed over the surface of thesubstrate, and a conductive layer disposed over the surface of theinterlayer film. In embodiments, the multilayer structure includes thesubstrate, the interlayer film on (i.e., directly on) the surface of thesubstrate, and a conductive layer on (i.e., directly on) the surface ofthe interlayer film. The conductive layer may be formed from aconductive composition. The conductive composition may include a varietyof materials, including metal nanoparticles. In embodiments, the metalnanoparticles include silver nanoparticles. Conductive compositionsincluding silver nanoparticles such as those disclosed in U.S. Pat. Nos.8,765,025; 8,361,350; 8,324,294; 8,298,314; 8,158,032; 8,057,849; and7,270,694 may be used.

After deposition and curing of the interlayer composition to form theinterlayer film as described above, the multilayer structure may beformed by depositing the conductive composition on or over theinterlayer film. Deposition may be accomplished by a variety oftechniques, including solution-based deposition techniques, as describedabove with respect to the interlayer composition. In embodiments, thedeposited conductive composition is subsequently annealed to form theconductive layer. Annealing may be used to provide a conductive layerincluding sintered metal nanoparticles, e.g., sintered silvernanoparticles. Annealing may be accomplished via a variety oftechniques, including, for example, thermal heating, radiation withlight (e.g., infrared, microwave, ultraviolet), and the like.

The conductive layer need not fully cover the surface of the underlyinginterlayer film. For example, depending upon the deposition technique,the conductive layer may include a plurality of conductive featuresarranged according to a pre-determined pattern or design. Conductivefeatures include, for example, electrodes, pads, interconnects, traces,lines, tracks, and the like. Inkjet printing is a deposition techniquethat may be used to provide such conductive features.

Additional material layers may be included in the multilayer structure.The multilayer structure may be part of an electronic device (or acomponent thereof). Electronic devices, include, for example, thin filmtransistors, light emitting diodes, RFID tags, photovoltaics, displays,printed antenna, and the like.

As described above, in embodiments, the interlayer films provideexcellent adhesion of conductive layers to an underlying substrate,while maintaining the desired properties of the conductive layers,including the conductivity of the conductive layers. In embodiments, theconductivity of the conductive layer in the multilayer structure isgreater than about 100 Siemens/centimeter (S/cm), in embodiments greaterthan about 1000 S/cm, in embodiments greater than about 2,000 S/cm, inembodiments greater than about 5,000 S/cm, in embodiments greater thanabout 10,000 S/cm, or in embodiments greater than about 50,000 S/cm.This includes embodiments in which the conductivity is in the range offrom about 6×10⁴ S/cm to about 2×10⁵ S/cm. Conductivity may be measuredby measuring the volume resistivity of the conductive layer with acommercially 4-point probe apparatus (e.g., from Cascade Microtech,Inc.). Conductivity=1/Resistivity. In embodiments, substantially none ofthe conductive layer is removed during an adhesion test. An adhesiontest is described in the Examples below. By “substantially none,” it ismeant that no conductive layer is removed under visual inspection.

EXAMPLES

The following Examples are being submitted to illustrate variousembodiments of the present disclosure. These Examples are intended to beillustrative only and are not intended to limit the scope of the presentdisclosure. Also, parts and percentages are by weight unless otherwiseindicated. As used throughout this patent specification, “roomtemperature” refers to a temperature of from about 20° C. to about 25°C.

Interlayer Compositions

Interlayer compositions were formed by mixing together the components atthe amounts shown in Table 1. The amounts are given as weight percent bytotal weight of the interlayer composition.

TABLE 1 Formulations of the Interlayer Compositions. Component Sample 1Sample 2 Multi-functional Acrylate Monomer 79.6 79.6 (SR-9003B, SartomerCo. Inc.) Acrylate Oligomer 1 12.2 — (SD-5907, DIC Corporation) AcrylateOligomer 2 — 12.0 (SD-661, DIC Corporation) Photoinitiator 1 6.5 6.7(Irgacure-184, BASF) Photoinitiator 2 1.7 1.6 (Irgacure TPO-L, BASF)Total 100 100

Interlayer Films

The interlayer compositions were deposited onto pre-cleaned glassmicroscope slides or polyethylene naphthalate substrates using a SCSP6700 Spin Coater. The coating speed was set at 100 rpm for 5 seconds,then increased to 1600 rpm and kept at this speed for 60 seconds. Thespin coated samples were UV cured using a Fusions UV 600 Lighthammerequipped with a D bulb mercury lamp on a moving track at 32 fpm beltspeed. The area of exposure was 12 inches. Thus, the curing time per 12inches was 1.875 seconds. The curing was conducted at room temperatureand in air at atmospheric pressure.

Conductive Layers

A conductive composition including 15% solids silver nanoparticles wasspin coated onto the interlayer films using the same conditions asdescribed for the interlayer films. Comparative samples were formed byspin coating the conductive composition directly onto the substrates(i.e., no interlayer film). The spin coated samples were then annealedat 120° C. for 10-30 minutes.

Curing Test

To test if the interlayer films were fully cured, the surface of theinterlayer films were rubbed using a sponge tip moistened with isopropylalcohol and the sponge tip visually evaluated. No marks or smears on thesponge tip indicated complete curing. Interlayer films formed from theinterlayer compositions were fully cured.

Adhesion Test

The resulting conductive layers were subjected to an adhesion test bysticking Scotch® Magic™ Tape to the surface of the conductive layers,then peeling the tape off of the surface, and visually evaluating thetape. For the comparative samples without any interlayer film, theadhesion of the conductive layers was very poor, resulting in a largeamount of the conductive layer peeling off the substrate and onto thetapes. For the samples with the interlayer film, the adhesion of theconductive layers was very good, resulting in no conductive layer orinterlayer film peeling off the substrate and clear tapes.

It will be appreciated that variants of the above-disclosed embodimentsand other features and functions or alternatives thereof, may becombined into many other different systems or applications. Variouspresently unforeseen or unanticipated alternatives, modifications,variations or improvements therein may be subsequently made by thoseskilled in the art, which are also intended to be encompassed by thefollowing claims.

What is claimed is:
 1. A multilayer structure comprising: a substrate; an interlayer film on the substrate, the interlayer film formed from a UV curable interlayer composition comprising at least one aliphatic di(meth)acrylate monomer diluent having a dynamic viscosity at 25° C. of less than about 100 eps; at least one (meth)acrylate oligomer selected from epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates and combinations thereof, the at least one(meth) acrylate oligomer having a glass transition temperature in the range of from about minus 10° C. to about 100° C. and a dynamic viscosity at 25° C. of less than about 3000 cps; and at least two photoinitiators; and a conductive layer on the interlayer film, the conductive layer comprising sintered metal nanoparticles.
 2. The multilayer structure of claim 1, wherein the sintered metal nanoparticles comprise sintered silver nanoparticles.
 3. The multilayer structure of claim 1, wherein the average thickness of the interlayer film is less than about 15 μm.
 4. The multilayer structure of claim 1, wherein the interlayer film has a Tg in the range of from about minus 10° C. to about 100° C.
 5. The multilayer structure of claim 1, wherein the interlayer film has a Young's modulus at room temperature in the range of from about 0.2 kgf/mm² to about 1 kgf/mm².
 6. The multilayer structure of claim 1, wherein the conductive layer exhibits a conductivity in the range of from about 6×10⁴ S/cm to about 2×10⁵ S/cm.
 7. The multilayer structure of claim 1, wherein the interlayer film has a surface free energy at 25° C. of from about 23 mN/m to about 43 mN/m.
 8. The multilayer structure of claim 1, wherein the interlayer film has an instant water contact angle at room temperature of from about 45 degrees to about 105 degrees.
 9. The multilayer structure of claim 1, wherein the interlayer film exhibits each of the following properties: a Tg in the range of from about 25° C. to about 35° C.; a Young's modulus at room temperature in the range of from about 0.2 kgf/mm² to about 1 kgf/mm²; a surface free en ergy at 25° C. of from about 23 mN/m to about 43 mN/m; and an instant water contact angle at room temperature of from about 45 degrees to about 105 degrees.
 10. The multilayer structure of claim 1, wherein the at least one aliphatic di(meth)acrylate monomer diluent is an alkoxylated neopentyl glycol di(meth)acrylate.
 11. A multilayer structure comprising: a substrate; an interlayer film on the substrate, the interlayer film formed from a UV curable interlayer composition comprising at least one aliphatic di(meth)acrylate monomer diluent having a dynamic viscosity at 25° C. of less than about 100 eps; at least one (meth)acrylate oligomer selected from epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates and combinations thereof, the at least one(meth) acrylate oligomer having a glass transition temperature in the range of from about minus 10° C. to about 100° C. and a dynamic viscosity at 25° C. of less than about 3000 cps; and at least two photoinitiators, wherein the interlayer composition comprises from about 60% to about 95% by weight of the at least one aliphatic di(meth)acrylate monomer diluent, from about 3% to about 20% by weight of the at least one (meth)acrylate oligomer, and from about 1% to about 10% by weight of the at least two photoinitiators; and a conductive layer on the interlayer film, the conductive layer comprising sintered metal nanoparticles.
 12. The multilayer structure of claim 11, wherein the interlayer composition comprises the ratio of the at least one aliphatic di(meth)acrylate monomer diluent to the at least one (meth)acrylate oligomer is in the range of from about 4:1 to about 16:1.
 13. The multilayer structure of claim 11, wherein the at least one aliphatic di(meth)acrylate monomer diluent is an alkoxylated neopentyl glycol di(meth)acrylate.
 14. The multilayer structure of claim 11, wherein the at least one aliphatic di(meth)acrylate monomer diluent is selected from alkoxylated neopentyl glycol di(meth)acrylates, alkyldiol di(meth) acrylates, alkoxylated alkyldiol di(meth)acrylates, alkyl glycol di(meth)acrylates, and combinations thereof.
 15. The multilayer structure of claim 11, wherein the at least one aliphatic di(meth)acrylate monomer diluent is an alkoxylated neopentyl glycol di(meth)acrylate and the alkoxylated neopentyl glycol di(meth)acrylate is selected from ethoxylated neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, and combinations thereof.
 16. The multilayer structure of claim 11, wherein the at least one aliphatic di(meth)acrylate monomer diluent is propoxylated neopentyl glycol diacrylate.
 17. The multilayer structure of claim 11, wherein the at least one (meth)acrylate oligomer is selected from epoxy acrylates, polyether acrylates, urethane acrylates, and combinations thereof.
 18. The multilayer structure of claim 11, wherein the interlayer composition consists essentially of one or more types of the aliphatic di(meth)acrylate monomer diluents; one or more types of the (meth)acrylate oligomer; two or more of the photoinitiators; optionally, one or more types of surface leveling agents, optionally, one or more types of curing accelerators, optionally, one or more types of surfactants; and optionally, one or more types of mono-functional (meth)acrylate monomer diluents. 